Process for gas making



May 1,1923.

H. R. BERRY PRobEss FOR GAS MAKING Filed March 22, 1923 r a; M N N m. Nm B Patented May 1, 1923.

HAROLD R. BERRY, OF BROOKLYN, NEW YORK, ASSIGNOR TO PETROLEUM RESEARCH IAND BY-PRODUCTS COMPANY, OF WILMINGTON, DELAWARE, A CORPORATION OFDELAWARE.

PROCESS FOR GAS MAKING.

To all whom it may concern:

Be it known that I, HAROLD R. BERRY, a citizen of the United States,residing at Brooklyn, in the county of Kings and State 5 of New York,have invented certain new and useful Improvements in Processes for GasMaking, of which the following is a full, clear, and exact adescri tion,such as will enable others skilled in t e art to which it appertains tomake and use the same.

The object of this invention is the manufacture of non-toxic combustiblegas. process contemplates substituting for carbon monoxide, byelementary chemical reaction, gaseous material equally high in thermalunit value and not possessed of the toxic detriment. Though certainmaterials, sustaining reactions utilized are found at certain periods ofthe operation substantially unchanged, this function of the process isnot to be classified as due to catalysis, but as the occasion of dualreaction in which a second reaction effaces the product of the first.

As carbon dioxide is an inert, non-combus- 25 tible gas and as themonoxide yields thermal value when burned, universal practice prescribesmaximum yield in monoxide and minimum production of dioxide quantitiesin gas making.

The claim presented is that the practice is not sound; that under coalbed conditions for artificial gas production, total quantities of heatunits available from combustion of resultant gases are reduced, notincreased, by occurrence of carbon monoxide quantities.

No attempt will be made herein to enumerate the various substancessusceptible of use as reagents, but a sin le material will be indicatedillustrative of t e class. 7

Though the recess may be applied to the various metho s by which thevariety of carbon monoxide containing gases are produced, no attempt,however, will be made to show specific application in each case, butapplication of the process will be shown with respect to a specific gas,water gas, for instance, as illustra- The" tive of the application ofthe process to the gas making art.

The apparatus presented is not necessarily the most eflicient, butpossibly, the simplest from the standpoint of minimum change needed instandard equipment, for utilizing f the process presented.

It is only within extremely few localities that water gas is suppliedfor public consumption without enrichment, hence presentment of thepresent process is carried in its operation through carburettor andsuperheater and to the production of an enriched water gas sufficient inthermal value to satisfy the customary local requirement of 525 B. t. u.per M. cubic feet of gas.

The novelty of the invention includes not only the reactions involved inproducing a final, commercial, enriched water gas product .but alsoproduction with certain additions and modifications in the manner watergas is produced, of gas manufactured. after the fashion of water gas,substantially freed, however, of carbon monoxide.

There is presented in Figures A, B and C, I

substantially in cross section, I a generator.

carburettor and super-heater standardized as the elements in water gasgeneration. In the generator Figure A, the top oi its interior as usedin practice is shown by dot and dash line 10F1gure A, and no opening 17nor pipe 24Figure A is customarily in use.

The grate for sustaining bonaceous material in the Y enerator isindicated l-Figure A. A c arge of carbonaceous material on this grate isheated to incandescence by means of a blast delivered, for instance,through intake 2-Figure A. The direction taken bythe combustion productsand heat values during the blow period is through pipe 21Figure A shownin dot and dash line. Thecourse may then be downward through thecheckerbrick structure of the carburettor Figure ,B, throu h connectingpipe 4Figure B, through tie checkerbrick structure of the super-heaterFigure C; thence, through stack 5-Figthe bed of carure C. During thisblasting or blowing period, the three "apparatus elements are heated tothe needed temperature for the subsequent operation of gas-making; whenthe inlet of air is discontinued by means of a valve shut-oil", notshown, and the opening 2Figure A is closed, and steam is deliveredthrough opening 3Figure A.

The familiar process then follows of hydrogen released from steam (H O),oxidation of the carbon of the coal into CO and CO delivery of theresultant gases into contact with enriching oil supplied through sprayer6, element B, and conduction t rough pipe 4 for fixation in element C,thence finding exit through pipe 7 element 0 and through various devicesfor scrubbing, washing and purifying to the gas holder.

Application of the process presented may be had by addition to thestandard water gas manufacturing methods by, for instance, adding to thetop of the generator Figure A a shell-Figure D of any suitable materialand type of construction. This shell possesses a top 8-Figure D, and abottom 9Figure D, through which is cut a hole 11Figure D, installed inthe bottom of which is a mesh grating 12-Figure D, The customarily usedpipe 21Figure A is eliminated and pipe 24Figure A is supplied. Pipe13Figure D is installed connecting the interior of Figure D with theinterior of carburettor Figure B. Figure D is supplied at its uppermostpart with inlet 14 and cap valve 15. There is also added to Figure A anintake or chute of suitable size 16-Figure A equipped with valve or gate17Figure A. 18 and 19. represent any suitable means of brace and supportfor the added member-Figure D; 22 represents a working platform.

In utilizing the process presented in the apparatus indicated, there issupplied through intake I l-Figure D, upon grate 12-Figure D in finelydivided parts shavings, strips and borings of any material which, underthe heat conditions established in water gas generation, will react withsteam forming an oxide and releasing hydrogen, and also, in the presenceof carbon monoxide under like conditions, will give up the oxygenacquired in the initial oxidizing step to the carbon monoxide of thewater gas, forming carbon dioxide and thus itself returning to its ownunoxidized, free condition, as, for instance, scrap steel and ironborings and shavings.

The quantity requirement of such material is governed more by theavailable surface contact afforded by small physical division, ratherthan by mass. This is true because the steam which oxidizes, forinstance,

steel and iron shavings and borings is accompanied with carbon monoxide,the almost simultaneous reaction of which is to deoxidize the oxides ofthe reagent into primary, metallic, free state.

The steam oxidizing the iron and steel material with hydrogen release,and the car- In operation.

As to the availability of heat for effecting needed temperature of thematerial deposited -upon grate 12Figure D, it will be foundsubstantially correct and within the bounds of practice to state that inoperating, for instance, any standard twelve foot diameter water gasunit, there is delivered during the blow period some 25,000 cubic feetof air per minutean average length of such period approximates 2%minutes and a pyrometer placed at the exit of the super-heater Figure Cwill register above 1400 F. throughout the blow, a quantity of heat ispresent, so great as to render practically negligible any heatabsorption requirement by the reagent employed in the operation ofFigure D.

In the gas making run it is customary to deliver through intake 3-FigureA steam in amount greater than the reaction requirements occurrent byits passage through grate 1-Figure A.

The reason for this is that the practice is to regard an increase ofsteam volume through the carbon bed 1Figure A as increasing the COvalues with curtailment of CO quantities. CO in combustion possessingabout 323 B. t. u. per cubic foot and ()0 bein inert, economy seemsapparent.

The foll owing facts appear, however, completely at variance with thepractice.

Results of observation, fully corroborated by much literature on thesubject show that at about 600 cent. the reaction of oxygen and carbonyields, within about 3%, a total CO quantity. As the temperature isincreased, monoxide values increase until at somewhat over 1000 cent.the reaction of carbon and oxygen yields but a little over 3% of COTemperature rather than steam quantities seem to govern.

The foregoing has furnished the foundation for the familiarly presentedhypothesis that all primary oxidation reactions of carbon are to CO andthat the occurrence of monoxide quantities is due to increased atomicreaction energy induced by elevated temperature; whereby the dioxidemolecule in the presence of excess carbon produces the reaction C+CO:2CO.

-An interestin table ofobservations will befound in Gas ThigineeringPractice, Latta, page '10, Van Nostrand 1907, in which not onlytemperatures, but rates of steam flow are contrasted under difi'eringconditions. from which it appears that, temperatures remaining constant,increased rate'of steam flow increases CO quantities.

In this eifect produced by speed regula tion of steam flow is to befound the steam quantity precept of present practice, which means thatit follows as a necessity that through a pipe of fixed diameter a largerquantity must move withgreater velocity than a lesser. When steamquantities are increased within the generator beyond reactionrequirements velocity is augmented proportionately with the increase.

The endothermic character of water gas generator reactions and theheatabsorption by prescribed quantities of undecomposed steam passingthrough'the carbon bed must thereby reduce temperatures and COquantitative recoveries.

' Furthermore, even though maximum CO g values could be recovered inaccordance with the effort of present practice, it appears that thenumber of units of combustive value in the resultant gas would not beincreased. And the reason for this is as follows:

' It is to be observed in water gas manufacture, that the element oxygenoccurrent in the CO and CO, product gases is derived fromI-LO'. It isimpossible to obtain oxygen from this source forcombining with carbonWithout releasing,"as free hydrogen, the coefliciental quantity ofhydrogen from the H 0 molecule. n every such molecule (H O) there isalways by weight of hydrogen to the amount of oxygen.

Thus, if 12 pounds of C is in combination with 16 pounds of oxygen,there is formed 28 pounds of carbon monoxide. But, to obtain the 16pounds of oxygen, i; of that amount by weight must have been liberatedas h drogen, or 2 pounds of hydrogen, or the 1 1 0 pounds in the form ofsteam must be the sum of these which is O16 lbs.+ H-2 1bs. 18 lbs. H O.

The quantities and thermal values involved are these:

'121t.ot0oo=?5 4u.a. and 24.3670 Btu. Had the reaction of the 12 lb. ofcarbon been entirely to carboni dioxideihstead of to carbonmonoxide',the result would be: I

121b.Ot oCO, 1126 cu.ft. and 245152 B. t. u.

The reaction to CO 'cOmpared with the reaction to CO, while yieldinggreatly in creased carbon dioxide quantities and greatly increased gasvolume, nevertheless, shows in the free hydrogen content, a total B. t.u.

thermal value which is at least the equal of tioned, that at lowtemperatures with an initial heat condition of approximately 600 cent.large hydrogen and dioxide quantities are produced. The reason forlimiting the as making period in water gas manufacture is that, as thetemperature falls in the grate, the dioxide quantities increase; hence,the supply of steam is discontinued and a blow period begins. As it isnot the purpose in the process under discussion to recover monoxidevalues, but to liberate large quan-" tities of hydrogen through theproduction 'of dioxide, the steaming period'continues to lowtemperature. To a temperature,-in fact, limited only by heatavailability for converting the steam in contact with the carbon intofree hydrogen and dioxide.

Practice and calculation easily demonstrate the fact that only between30 and 35% of the carbon bed charge is available for reaction in Watergas manufacture. The remaining and far greater part of the charge isconsumed in producing through combustion high heat conditions requiredin the manufacture of carbon monoxide. It becomes completely evidentthat in utilizing the process presented, the steaming period of the runis not discontinued around 2000 F., but is continued even to so lowatemperature that practically the entire carbon bed yield may behydrogen and dioxide. Thus, instead of approximately one-third of thecoal bed charge entering into gas producing reactions, it is found thatan-increased percentage of such charge is so available. This producesenormous increase in the total volume of gas produced from likequantities of carbon charge supplied. A second step in the processpresented includes the use of a reaction zone supplied with suitablereagent material which will oxidize under the conditions establishedinto an oxide, which oxide will part with its oxygen to carbon monoxide,producing carbon dioxide, thus rejuvenating itself.

Operation of this second function of the process may be had by deliveryupon grate l2l*igure D, of scrap iron and steel filing or borings, orother suitable material through which the gaseous products from thewater gas generator grate are conducted.

Acompanying the gaseous products through grate 12-Figure D are steamquantities delivered, for instance, through pipe 2l-Figure A in amountsufiicient to produce some or all of the following reactions:

Such carbon monoxide quantities as are produced from grate l-Figure Acontact the oxidized reagent material with one or more of the results:

F00 +oo' =Fe +00, F9203 300 2Fe 3002 F6 0, 400 3Fe 400 The oxides formedthrough the agenc of steam are thus eft'aced by giving up tieir oxygenfor oxidization of carbon monoxide into carbon dioxide and the materialis coincidently serviceable for re-oxidation, hydrogen re ease andcontinuity of repetition.

In operating this second function of the process, a reversible reactionproblem is presented by (ontacting hydrogen, carbon monoxide, steam andsuch a reagent material as iron.

In solving this problem it is again found that temperatures andproportions are the controlling factors. Experimental observation andliterature on the subject establish, within practical limits, theaccuracy of the following:

At 400 F. X cubic feet of hydrogen plus X cubic feet of steam passthrough a ferrous reagent material without respective quantitive change.Any excess of steam over the 20 :1 ratio yields a co-eflicientalquantity of equal amount as iron oxides and free hydrogen.

At 800 F. the ratio for balanced reaction with no quantitive alterationin material supplied and resultants is 6 to 1, steam volume to hydrogenvolume. A steam quantity in excess of this ratio at this temperatureproduces hydrogen in pounds to the extent of the weight of hydrogen inthe steam exceeding the ratio. Eight times this weight in oxygencombines with the reagent material as oxides.

At 1200 F. the ratio is observed to drop approximately to a trifle under4 to 1, and each of the above statements apply for excess steam overthis ratio at this temperature.

At 1600 F. likewise in other respects as above the ratio approximates2:1.

At 2000 F. nearly 3 :2.

At 2400 F. virtually 1 :1.

Beyond this temperature even with selected material, eliminating whitecast iron and hard steel, it is difficult to avoid the tendency to meltand fuse, but it'may be safely said that at approximately 2750 F. thelarger quantity of the ratio is in favor of the hydrogen. The curve isas follows:

STERN-HYDROGEN AflT/O Thus, to preserve without reaction, hydrogenquantities emanating from the coal bed and passing through the reagentmaterial,

there must be supplied an amount of steam bearing ratio to the volumequantity of hydrogen as generally shown by the preceding curve. Withthiscondition met, the

excess steam. requirement in pounds and the product .gas in volume isderivable as follows:

c. f. H c. COc.f. l i co f 00 f i I Cu.ft. Water,gas-CO+2 x x X8.5+ 8XII 88 (a) X 3 gives in pounds of water equivalent the steam reactionrequirements of the reagent material.

However, it must be observed, as before compounds pass through thecarburettor unexplained, that as operation of the process obtains underlow heat condition of the carbon bed, the steaming period is thusprolonged. Therefore, the quantity cubic feet water gas above producedby the process presented is in a volume greater than the quantityproduction by present practice.

A third step contemplated within the operation of, the process is, whenadvisable, n-

i-ichment of the product gases emanating from. the generator grate andthrough the reagent material- No attempt is made in these specificationsto outline the various methods of gas enrichment which may be employed.The non-toxic, artificial gas produced by this process may be enrichedwith any suitable carbonaceous material, in gaseous, liquid or solidform, and to such extent that any degree of increased thermal value maybe achieved, even though the intensity of such enrichment producesvapors instead of gas within the carburettor. Enrichment may beaccomplished by methods customarily in practice for similar purposes,for instance:

. There is delivered through pipe 13--Figure 1): into carburettor FigureB product gases from ,Figures'A and D which are contacted with enrichingmate rial sprayed into. Figure B through sprayer. 6Figure .B -Theenriching material is, for instance, gas oil.

It is to be observed that this hydrogencarbon-dioxide gas enriches intorequired thermalvalue for commercial or other use with the addition ofless enriching material than is required by the present carbon monoxidecontaining commodity.

=The only constituent occurrent in a gas affected in this respect.

It is self-evident that a small percentage of hydrogen requires greaterenrichment to elevate the general average of a gas to a.

given requirement than is required to effect like result where thehydrogen content of the gas is greater. For instance:

14 pounds of hydrogen with 226 pounds of a gas oil, such as C H enrichesinto 240 pounds of ethane. 240 pounds of ethane is 3000 cubic feet ofgas, with a total B. t. u. value of 5,292,000; whereas, the samequantity of oil with 30 pounds of hydrogen will enrich into 256 poundsof methane, which is 6016 cubic feet, of a total B. t. u.-value of6,070,000.

The comparison presented is:

From the same quantity of oil, under intensive enrichment requirements,the volume 1921b. o+4s lbtH 240 lb. 0,11, q 240 lb. 0.11,:3000 cu.a.=5,292,oo0 B.

t. u. Same quantity 226 lb. C H enrich- I ing with hydrogen to methane.

C H 192 1b. 34 lb. Add 30 lb.

192 lb. c+e4 lb. H=256 lb. on,

256 lb. 0H,:6016 cu. ft.==6,070,144 B. t. u.

A fourth step to beincluded when ade visable in the operation. of theprocess presented, consists in the reduction to desired extent of thecarbon dioxide quantities of the resultant gas.

The effect of the presence of carbon dioxide on the candle power ofwater gas is well known. Even the occurrence of so small a percentage as22 causes a loss of nearly 10% in the theoretical candle poweravailable. The ratio increases until with a carbon dioxide contentsomewhat over onehalf by volume, the candle power efiiciency of the gasis virtually destroyed; whereas, the occurrence of carbon dioxidepercentage in a gas is a detriment to the heat units produced throughcombustion, nevertheless, the detrimental effect is minute in comparisonwith the effect on candle power.

For instance, a 528 B. t. 11. gas with so large a carbon dioxide contentas 33%,%. when combusted, will lose less than 15% of its theoreticalthermal yield based upon a flame temperature in excess of 1000 F. Thefigures are:

OIL- 16% (g -33% B. t. u. 528

2 CO, sp. heat i2163 0 Furthermore, it will be found that with a carbondioxide content of 10%, the thermal flame value loss by combustion ofthe gas is virtually negligible, being considerably under 17 Theeconomically unsound practice of rating gas .manufactured for publicconsumption on a candle power basis has virtually been discontinued. Thestandard requirements today are on a thermal unit basis and inconformity with such regulations, the gas manufactured by the processpresented is most useful.

It will be found that gas manufactured by the process presented willcontain up to 30% of carbon dioxide and in uses involving the combustionof the gas in a cold state, it may be found advisable to reduce thisquantit There are many familiar processes effectual for this purposeincluding the use of compounds of sodium, calcium and potassium.Possibly the cheapest and most convenient method is the reaction ofcaustic lime to the carbonate.

When the candle power standard governed gas values, much-effort was madeto rid the gas of even small carbon dioxide percentages. It is a knownfact that even so low as 5% carbon dioxide content reduces the candlepower of the gas by 20%.

In the use of caustic lime for this purpose, the many unsatisfactoryresults were found traceable to the difliculty of reducing smallquantities of carbon dioxide present. A gas containing a largepercentage of dioxi'de readily reacts and relinquishes such quantitiesup to a narrow residual of from 5 to 10%.

It has been shown above that so small a percentage of'carbon dioxide hasno appreciable effect upon complete recovery of the total thermal valueof the gas through combustion.

Thus, as the fourth step of the process, by suitable and customaryarrangement, the product gas should be passed through and in contactwith caustic lime or other suitable material to reduce the carbondioxide quantities to from 5 to 10% of the volume.

No .improvement is suggested herein for washing, scrubbing and purifyingthe gas and customary practice is prescribed. However, it should beremarked that when the excess and undecomposed steam quantitiesoccurrent in gas as manufactured by present practice is precipitated, alarge percentage of the impurities of the gas are precipitated.

As excess steam quantities have been delivered while gas making inaccordance with the process presented, between the coal bed of thegenerator and the reagent material employed, the customary purifyingefi'ect produced by condensation of excess steam quantities ismaterially augmented.

The various steps or phases of the rocess presented may be properlycomprehended under the five divisions mentioned hereinbefore.

It is to be observed, however, that dependent upon uses to which theincident combusti-ve ases may be put certain of the steps may beincluded or omitted in the manufacturing operation. When the productgases may be combusted under conditions whereby the initial heatincident to their manufacture is retained, it may be found advisable inmany instances to eliminate both the methods presented for enriching andreducing carbon dioxide quantities. \Vhere, however, it is the purposein the manufacture of the gas to combust the same from a cold state,employment of all of the steps of the operation indicated may be foundto be best practice.

By way of summary:

In the first step of the process, it has been shown that in theproduction of artificial gas by this process in the manner in whichwater gas is produced, that no regulation of operation is adopted toincrease carbon monoxide. That, so far as total thermal content of theresultant gas is concerned, no reduction occurs through the productionof carbon dioxide. Also, it has been shown that because of the lowertemperatures at which water gas may be produced when no regard is paidto the quantity of carbon dioxide occurrent, that larger volume yield ofgas results.

The second step of the process presents tities emanating from the coalbed into carbon dioxide quantities without theoretic thermal loss.

The third step of the process which consists in increasing the thermalvalue of the gas through carburization or enriching, has been shown torequire the addition of less carbonaceous material than is required forthe-enrichment of a carbon monoxide containing gas produced undersimilar circumstances.

The fourth ste of the process deals with any suitable met od forreducing to moderate proportion the carbon dioxide content and 1n thisconnection it has been remarked that large percentages of CO readily arereduced to small percentages under conditions quite im ractical forcompletely eliminating asmal percentage of the dioxide.

The fifth step of the process has been shown to contemplate the washing,scrubbing and purifying of the commodity along the lines of customaryusage.

There "follows a quantitative calculation of the operation of a standardgas making unit in accordance with present practice contrasted with theoperation of such a unit when modified and operated in accordance withthe specifications and drawings of these disclosures.

- Standard 152 ft. water gas set.

Standard practice .operation.

Daily blue gas production 4,000,000 ft.

Enrichment values gas oil about 3.8gals. for 525 B. t. u. per M-1 5,000gallons.

Daily enriched gas production 4,250,000

Y cu. ft.

. Estimates of precipitates from scrubbers, washers, purifiers, andcondensers, checkerbrick carbonization, nitrates, oxides, tars, wasteproducts and ingredients are eliminated as not materially germane tothese disclosures. All calculations are reasonably correct, butapproximate.

To facilitate examination a numeral is placed in front of each quantitywhen first derived and when referred to afterward the numeral followsthe'quantity for ready reference.

Hourly blue gas production Run composition (not considered exceptionallygood, 00 a trlfie high) hydrogen 53% carbon monoxide 41% carbon dioxide6%.

1 H 88,333 3. f. 2gb 469.82 lbs.

(3) CO 68,3340. f. 4 5032 lbs. 5 o 2139 lbs.

' 3 (a 2893 9 320 -1 =(8) 1177 lbs. 10 o 857 Obtained, approximately 500gallons water+2500 carbon, thus:

'H,O lb. H lb. 0 lb. 0 lb. 4219.82 469.82 3.750 +2489 H CO 5032 lbs. 4CO, 1177 lbs. (8)

An error of 1 lb. H is due to fractions not carried out. Thus, from thecarbon bed,- grate 1-Figure A, for instance, there H-469.82 lbs. (2)88,333 01 emanates under conditions shown in 1 hour of standard practiceoperation:

f. 1) 325 28,708,225 B. t. u. CO-5062 lbs. 4 68,324 3. f. (3) Go, 1177lbs. (8 10,000 0. f. 7

Blue gas 166,6670. f.

=304 B. t. u. Per 0. f.

22,071,882 No combustive value.

50,780,107 B. t. u.

of carbon monoxide per hour with associated blue gas components underoperating conditions prescribed.

Of the 5062 pounds (4) of carbon monoxide, 2893 pounds (6) are oxygen.For the monoxide uantity to react'into carbon dioxide an a ditional 2893pounds of oxygen is required. v

But for 2893 pounds of oxygen to be thus available oxygen to such anamount must be incorporated from steam (H O) releasing thereby in freestate its concomitant of hydrogen. For example 11,0 a o H 3254.6 lbs.(11) 2893 lbs. (12) 361.6 lbs.

Standard resultants.

H2 88333 c. f. (1) CO 68334 0. f. (3) CO, 10000 0. f. 7

Total volume-166,667 c. f.

B. t. 11. per fit-304 Process resultants.

1e) 2327,9313 O. f.

Total B. t. u. 50,780,000 50,800,000

The process gas is shown as rid of carbon monoxide. The total B. t. u.values remain unimpaired. The volume is increased not only by additionto the hydrogen content, but by large addition to the non-toxic, thoughnon-economic quantity CO Reactions within the carburettor aresubstantially as follows:

Supplied; process gas composed as above shown and gas oil for instancean oil of an average gravity and boiling point as typified byHexadecane-G,,,H

B. P. 549 F., sp. gr., .7319, wt. per gallon 6.07 lb. carbon (17) 5.157lb. per gallon hydrogen (18) .913 lb. per gallon.

There will be used during the one hour run by rocess methods 675 gallonsof this oil, resu ting thus within the carburettor:

Quantities supplied.

Hydrogen CO5 Carbon Methane Gas ..469.8lb. 2 77,617 0.1. 15

361.61b. 12 Oil 675 gallons 4097.25 pounds 616.4lb. 34811b.

Totals. ...1447.s 1b. 77,617 0.1. 3481 lb. Reaction quenmxeS 1160 lb,3431 lb. 4641 lb.

Volume cu. it B. t. u. Hydrogen 54100 17,584,450 Methane 1090-3110,044,567 00, 77617 Bmultant gas (19 240786 011- It. 20 127,029,017

2 83-530 B. t. u. per cu. ft. wg lJ gal. oil per M feet.

The foregoing is to be contrasted with operation in accordance withpresent practice. The quantities having been shown to pounds of carbonbe; gas produced 177,000 cu. ft., thermal value 525 B. t. 11.,enrichment requirement 3.8 gallons per M cu. ft. The process gas beingfree o'rmonoxide and the gas of pres ent practice containing upwards of68,000

cu. ft.

If the product gas' 240786' cu. ft. is reduced to approximately thevolume produced by standard practice operation, by reducing COconstituent in accordance with the methods of the fourth step of theproc ess, there results, approximately 180,000 cu. ft. of gas withlessthan a ten per cent CO content. The effect of. such uantity of CO hasbeen shown to be negligible upon heat unit production throughcombustion. The B. t. u. value of such gas, however, by such reductionof "the CO quantities has been raised from 525 B. t. u. gas to 710 B. t.u. per cu. ft. 7

Enrichment quantities have been figured 'on the basis of the valuesactually reacting into enriching gases and the quantity estimate forthis purpose should be increased to the extent of. loss-occasionedthrough carbonization withinthe enriching unit.

It is to be observed, however, that an loss so occasioned is more'tha-ncounterba anced by the increased thermal value of the resultant processgas through the reduction of carbon dioxide quantities.

Practical operation of the process becomes extremely simple by theobservance of two rules. First. in the event of the occurrence of carbonmonoxide quantities in the gas product, steam deliveries should beincreased... Second, upon the presence of excessive quantities ofundecomposed steam in the gaseous product, steam deliveries should bedecreased. The reasons for these regulations are these:

.With respect to the first, if the steam de liveries reacting upon thereagent material are insufiicient to rovide suificient oxide which willunite with the'monoxide quantities in the production of carbon dioxide,monoxide quantities will escape. The necessary solution is increase ofsteam delivery which will add to the quantity of oxidized ple whichremedies both conditions, namely,

line, of the generator, avoiding steam,

upon the appearance of monoxide quantities in the product gases,increase the steam delivery available for reaction upon the reagent;upon'the presence in the resultant gases of excess quantities ofundecomposed decrease the steam supply.

The essence of the process lies. not in aparatus, operation method oravailability of y-products, but in the production of a gas,

rendered non-toxic by the substitution of hydrogen for carbon monoxide,

thermal value lost in monoxide is gained in hydrogen.

Many different apparatus arrangements and structures are in mind,departing from the illustrative apparatus shown in the drawings. Incases, for instance, of s mall units and shallow beds, the reagentmaterial may be supported within the generator itself with necessarychanges to accommodate such installation. Suitable change may be made toermit the use of water gas units'in which eit er or both blast or steammay be delivered above or below the coal bed grate. A special element,such as B, may be installed upon the approximate foundation the need ofinstallation of coal chute and other changes. Steam available forreagent reaction may be supplied above or below the coal be sgrate ofthe generator or into other units. eries or alternating sequence ofmaterials may be installed supported and contacted with the gaseousmaterial present manner. the process involved as applicable to anyapparatus susceptible of such operation as to so that the in anysuitable It is the purpose hereof to presentfurther contacting richedgas, reaction values may descend the scale of rarefication even intovapors liquefiable at atmospheric conditions oftemperature and pressure.

The use of insulation is not shown in the drawings as it is not'requiredin presenting the process, but in practice any suitable material andconstruction may be used for'the purpose. 7

Reference to shavings, borings and filings, is not intended to restrictthe physical make up. of the reagent employed; porous or spongyformations or any other material form or arrangement may be ado tedwhich will afford necessary contact su ace.

It is understood that in the construction of the apparatus, blowers forincreasing velocity of gaseous material with respect to conditioning thetime element of'contact may be established at suitable locations withinthe apparatus.

It is further to be understood that in the event of the manufacture of agas contemplating the reaction between steam and petroleum fractionswhereby the resultant quantities are similar to those of water gasmanufactured from coal by containing hy-. drogen, carbon monoxide andcarbon 'dioxide quantities, that the process submitted is utilizableunder such circumstances. What removing to desired extent the carbonmonoxide by contacting the gas, steam and a reagent material which willoxidize with steam releasing hydrogen and which will deoxidize with thecarbon monoxide forming carbon dioxideland enriching said gas by furthercontacting with carbonaceous. ma-

terial and reducing the carbon dioxide content of the gas to determinedextent by contacting with absorbent material and freeing the gas ofother impurities by scrubbing, washing and purifying.

2. A process for producing an artificial combustible gas which consistsof reacting steam and carbonaceous material into hydrogen, carbonmonoxide and carbon dioxide, removing to desired extent the carbonmonoxide by ntacting the gas, steam and a reagent material which willoxidize with the steam releasing hydrogen and which will deoxidize withthe carbon monoxide forming carbon dioxide and enriching said gas bywith carbonaceous material and reducing the carbon dioxide content ofthe gas to etermined extent by contacting withreacting material, andfreeing the as of other impurities -by scrubbing, washmg and purifying.

8. A proces for producing a substantially and that with regulation, the

installation of fans or I the non-toxic combustible gas which consistsof reacting steam and carbonaceous material into hydrogen, carbonmonoxide and carbon dioxide, removing the carbon monoxide by contactingthe gas, steam and a reagent material which will oxidize with the steamreleasing hydrogen and which will deoxidize with the carbon monoxideforming carbon dioxide, and enriching said gas by further contactingwith carbonaceous material, and reducing the carbon dioxide content bysuitable means and removing other impurities py means of washing,scrubbing and puriying.

4:. A process for increasing production quantities in the manufacture ofcertain combustible gases which consists in contacting, under suitableoperating conditions,carbonaceous material and steam and producingtherefrom a mixture of hydrogen, carbon monoxide and carbon dioxide andcontinuing the operation to low temperatures conditioned only by theheat requirement for steam decomposition, enriching the said mixture bysuitable means and removing therefrom any prescribed amount of thecarbon dioxide quantities.

5. A process for increasing the production quantities of certainenriched combustible gases which consists in contacting, under suitableoperating conditions, carbonaceous material and steam and producingtherefrom hydrogen, carbon monoxide and carbon dioxide and continuingthe operation to low temperatures regardless of increasing carbondioxide quantities resulting and thereby causing a large increase in theamount of carbonaceous material entering into chemical reaction in thegas making, Which under high temperatures would have been consumed fortheir maintenance and thereby largely increasing the volume of the gasand the hydrogen content thereof, and enriching said gas with enrichingquantities reduced .because of increased hydrogen content.

6. A process for reducing enrichment requirements of certain combustiblegases which consists in reacting said gas with a reagent material undersuch conditions that the carbon monoxideis replaced by hydrogen of atleast equal thermal value, and enriching said gas with enrichingquantities reduced because of increased hydrogen con tent.

7. A process for producing an artificial gas substantially free fromtoxic properties due to the presence of carbon monoxide which consistsin manufacturing in any suitable manner water gas, eliminating therefromsubstantially all the carbon monoxide elements,

substituting therefor by use of a reagent material a B. t. u. equivalentof hydrogen and enriching the gas mixture to desired thermal value.

through chemical contact 8. A process for producing an artificial gassubstntially free from toxic properties due to the presence of carbonmonoxide, which consists in producing Water gas, passing the same to adouble conversion or noncatalytic agent and reducing the carbon monoxidequantities of the water gas, substituting for such reduction ofquantities a B. t. u. equivalent of hydrogen, and enriching to desiredextent the resultant gases.

9. A process for increasing the quantity production of enrichedconverted water gas, which consists in continuing the reactions of thecarbonaceous material and steam Within the generator to low temperaturesincreasing thereby the percentage of carbonaceous material entering gasmaking reactions contrasted with the amount consumed for heatgeneration, contacting the gas produced with a reagent material by whichhydrogen is substituted for substantially ally the carbon monoxidequantities, and enriching said gas with enrichment quantities reducedbecause of the increased hydrogen content.

10. A process for producing enriched artificial gas substantially freefrom toxic properties, which consists in operating a water gas generatorat low temperature to avoid the production of carbon monoxide quantitiesand supplying a reagent zone in which with the reagent such carbonmonoxide as is produced is eliminated and there is substituted in itsstead hydrogen possessing at least the equivalent of the thermal valueof the carbon monoxide, and enriching the resultant aseous product withenriching quantities re uced because of the increased hydrogen content.

11. A process for the manufacture of a combustible gas which consists inproducing a non-toxic gas of greater volume and higher thermal valuethan the quantity and richness of water gas produced from a likecarbonaceous mass by continuing the gasmaking period incident to watergas manufacture to low temperatures regardless of carbon dioxideincrease, and reacting the product gas in the presence of steam andreagent material so that hydrogen quantities are substituted for carbonmonoxide quantities of no less volume or thermal value and enriching thesame by re-contact with carbonaceous material.

12. A process for reducing the cost of artificial gas production whichconsists in causing a larger percentage of a carbonaceous mass to enterinto gas-making chemical reaction than obtains in the standard methodsof Water gas production by continuing the gas-making run to lowtemperature and enriching the resultant gas with less additionalcarbonaceous material than is required in standard water gas operationsbecause of the hydrogen content in the resultantgas, and reducing thequantity of resultant carbon dioxide to desired amount by contact withsuitable material.

13. A process for modifying and enriching carbon monoxide containingsists in converting carbon monoxide into carbon dioxide by any suitablemeans with hydrogen release, and contacting the modified gas withcarbonaceous material thereby enriching the hydrogen content thereof toany desired extent, and reducing the carbon dioxide content of suchmodified gas to substantially any desired extent by reacting with anysuitable material.

14. A process for modifying and enriching carbon monoxide containinggas, which consists in converting carbon monoxide into carbon dioxide byany suitable means with hydrogen release and enriching the modified g15. A process for increasing the volume andthermal value of combustiblegas recovery from carbonaceous material, which consists in reactingcarbonaceous material and steam under high temperature produced byinternal combustion, continuing contact of said substances tosubstantially a temperature at which reaction fails and causing greaterincorporation of carbonaceous material into the gas-making reaction thanwhen reaction is stayed at higher temperature, enriching the resultantgases by recontact with carbonaceous material, of which reducedquantities are required because of increased hydrog the carbon dioxidecontent and impurities present, when necessary, by any suitable means.

16. A process for producing a substantially non-toxic combustible gasfrom carbonaceous material and steam, greater in volume and thermalvalue than that of water gas producible from like quantities, whichconsists in operating. a water gas generator during the gas-making runto low temperature, substantially that fails, increasing thereby thecarbon dioxide and hydrogen quantities and converting substantially allof the reduced carbon monoxidevalues into carbon dioxide and hydrogen,

gas, which con en content, and reducing.

at which reaction.

the hydrogen of substantially the same volume and thermal value as thecarbon monoxide converted, through reaction within a reagent zonesuitably equipped and operated with a reagent material and steam, sothat the reagent is oxidized releasing hydrogen and is dioxidiz'edforming carbon dioxide and rejuvenating itself, and enriching theresultant gas by contacting with carbonaceous material and reducing, ifnecessary, carbon dioxide and impprities present by suitable means.

17. A process for producing a non-toxic combustible gas fromcarbonaceous material and steam, reate'r in volume and thermalvaluefthan t at of water gas produced from like quantitites, whichconsists in operating a water gas generator during the gas-making run tolow temperature, to substantially that at which reaction fails causingthereby increase of the" quantity. f carbonaceous matter entering 'gasmaking reactions and decreasing the amount of carbonaceous matterrequired for heat production and increasing thereby the production ofcarbon dioxidev and hydrogen quantities and converting the reducedcarbon monoxide values into carbon dioxide and hydrogen, the hydrogenbeing of substantially the same volume and thermal value as the carbonmonoxide converted,

through reaction within ably equipped 1 material and steam so that thereagent is oxidized releasing hydrogen and is dioxia reagent zonesuitand operated w-1th a reagent dized forming carbon dioxide andrejuvenat-' ing itself, and enriching the resultant gas by contactingwith carbonaceous material and removing therefrom by suitable means thecarbon dioxide content to selected amount and effecting, to necessaryextent, elimination of any toxic uantities and impuritiqs presentthrough t e agency of washers, scrubbers and purifiers.

In testimony whereof inthe presence of two witnesses.

' HAROLD R. BERRY."

Witnesses: v

E. S. SUFFERN, .T. E. HARDING, JR.

